Herbicidal compositions containing uracil thiocyanate addition compounds



United States Patent O 3,300,292 HERBICIDAL COMPOSITIONS CONTAINING URA- CIL Tl-HOCYANATE ADDITION COMPOUNDS Raymond W. Luckenbaugh, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Filed July 1, 1965, Ser. No. 468,956

4 Claims. (Cl. 712.5)

where v R is alkyl of 1 through 10 carbon atoms,

substituted alkyl of 1 through 8 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, hydroxy, alkoxy, alkoxycarbonyl, dialkylamino, and cyano, aryl of 5 through carbon atoms, substituted phenyl of 6 through 14 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenylalkyl of 1 through 6 carbon atoms, chloroalkoxy of 1 through 5 carbon atoms, trifiuoromethyl, 1,2-tetramethylene, and 1,2-trimethylenylene, arylalkyl of 5 through 13 carbon atoms, substituted arylalkyl of 5 through 13 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl and alkoxy, alkenyl of 3 through 8 carbon atoms, alkynyl of 3 through 8 carbon atoms, cycloalkyl of 3 through 12 carbon atoms, substituted cycloalkyl of 3 through 12 carbon atoms, wherein saidsubstitutent is selected from the group consisting of bromine, chlorine, methoxy and alkyl, cycloalkenyl of 4 through 12 carbon atoms, 1 1 substituted cycloalkenyl of 4 through 12 carbon atoms, where-in said substituent is selected from the group consisting of bromine, chlorine, methoxy and alkyl, cycloalkyl alkyl of 4 through 13 carbon atoms, (substituted cycloalkyl)alkyl of 4 through 13 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy and alkyl, cycloalkenyl alkyl of 5 through 13 carbon atoms, (substituted cycloalkenyl)alkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy and alkyl, R is hydrogen, halogen, nitro, hydroxymethy1,

branched or unbranched alkyl of 1 through 6 carbon atoms, or alkoxymethyl wherein alkoxy contains 1 -M(SON)2 through4carbon atoms; I g R is hydrogen, methyl, chloromethyl or bromomethyl;

' these uracil addition compounds are not known.

R is hydrogen or branched or unbranched alkyl of 1 through 4 carbon atoms;

X is oxygen or sulfur;

M is magnesium, calcium, strontium, or barium; and

n is 1 or 2,

with the provison that R and R can be joined together to form an alkylene bridge of 3 through 5 carbon atoms.

It should be understood that the exact formulae of On the basis of the best available information, it is believed the elements have the configuration shown in Formula 1, but it is intended that this invention embrace these addition compounds whatever their structure, and Formula 1 should therefore not be construed as limiting.

In Formula 1 the term substituted alkyl is intended to include such radicals as bromoalkyl of 1 through 8 carbon atoms chloroalkyl of 1 through 8 carbon atoms hydroxyalkyl of 1 through 8 carbon atoms alkoxyalkyl of 2 through 8 carbon atoms alkoxy carbonyl alkyl of 3 through 8 carbon atoms diaalkyl amino alkyl of 3 through 8 carbon atoms and cyanoalkyl of 2 through 8 carbon atoms Similarly, the terms aryl and substituted phenyl? embrace radicals such as phenyl naphthyl O-biphenyl pyridyl chlorophenyl The terms arallcyl and substituted aralkyl are intended to include such radicals as benzylv phenylalkyl of 8"through 11 carbon atoms (total) chlorobenzyl dichlorobenzyl alkylbenzyl of 8 :through' 11 carbon atoms (total) diallrylbenzyl of 9" through 13 carbon atoms (total) nitrobenzyl alkoxybenzyl of Stbrough 11 carbon atoms (total) naphthylmethyl and furfuryl The terms-cycloalkyl, cycloalkenyl, cycloalkyl alkyl, and cycloalkenyl alkyl will incude cyclohexyl cyclohexenyl cyclohexylalkyl cyclohexenylalkyl cyclopentyl cyclopentenyl cyclopentylalkyl cyclopentenylalkyl norbornyl norbornenyl norbornylalkyl norbornenylalkyl bicyclo (2,2,2) octyl bicyclo (2,2,2) octenyl bicycle (2,2,2) octylalkyl bicyclo (2,2,2) octenylalkyl cyclopropyl cyclobutyl cyclobutylalkyl cyclobutenyl cyclobutenylalkyl hexahydroindanyl tetrahydroindanyl hexahydroindenyl hexahydroindenyl alkyl tetrahydroindanyl alkyl hexahydroindanyl alkyl hexahydro-4,7-methanoindenyl tetrahydro-4,7-methanoindanyl hexahydro-4,7-methanoindanyl hexahydro-4,7-methanoindanyl alkyl tetrahydro-4,7-methan-oindanyl alkyl hexahydro-4,7-methanoindanyl alkyl decahydronaphthyl decahydronaphthyl alkyl tetrahydronaphthyl tetrahydronaphthyl alkyl decahydro-l,4-methanonaphthyl decahydro-1,4-methanonaphthyl alkyl octahydro-1,4-methanonaphthyl octahydro-1,4-methanonaphthyl alkyl decahydro-l,4-5,8-dimethanonaphthyl decahydro-l,4,-5,8-dimethanonaphthyl alkyl octahydro-1,4-5,8-dimethanonaphthyl and octahydro-l,4-5,8-dimethanonaphthyl alkyl These cyclic substituents can be further substituted with alkyl groups of 1 through 4 carbon atoms, methoxy, chlorine and bromine.

The above-described addition compounds are prepared by reacting the appropriate uracil with a suitable thiocyanate.

The uracil reactants are prepared according to the following equations:

O acid (substituted urea) (fl-keto ester) (ureido ester intermediate) 0 9 X B 0 l RNHgNH C lOR'-- R l A RFN 2 won X N Ra M e O I Rs acid R X: N R3 M X B3 The l-alkyl substituted uracil reactants are then prepared from these tri-substituted uracils by ordinary substitution reactions with alkyl sulfates.

Preparation of suitable uracil reactants is set forth in greaterdetail in copending application Serial No. 364,309,

4 filed May 1, 1964. Those portions of that application showing preparation of suitable uracial reactants is incorporated by reference into this application.

The compounds of the invention are prepared by mixing 4 to 16 parts by weight of a 3560% aqueous solution of a thiocyanate with a dry uracil at room temperature. Reaction is immediate. The addition compounds precipitate and are filtered from the reaction medium. They are then washed with an organic solvent such as ether or pentane and dried in vacuo over a dehydrating agent such as P 0 or CaCI The uracil-thiocyanate addition compounds hereof have a herbicidal effect similar to that of the uracils per se. These addition compounds have been found, however, in accordance with the present invention to provide important formulating and handling advantages and thus herbicidal compositions of these compounds are preferred in various herbicidal applications. In particular, it is found that these uracil-thiocyanate addition compounds have melting points usually greater than 300 C. which permits preparation of wettable powders having high concentrations of active ingredients and also makes sand-grinding of liquid formulations easier and more stable.

These novel addition compounds, as the corresponding uracils per se, can be used as general-purpose weed killers, as soil sterilants, in soil-foliage applications, and as selective weed killers for either preor post-emergence weed control. The compounds control both annual and perennial broadleaf weeds and grasses.

When applied pre-emergence, the compounds control such germinating broadlea-f weeds as pigweed, lambsquarters, mustard, chickweed, flower-of-an-hour, ragweed and such grass weeds as crab grass, water grass, giant foxtail, green foxtail and seedling Johnson grass.

In soil-foliage applications, the compounds control existing mixed annual and perennial vegetation composed of such broadleaf and grass Weeds as crab grass, foxtail, water grass, quack grass, Bermuda grass, Johnson grass, brome grass, ragweed, cocklebur, pigweed, lambs quarters, mares tail, wild carrot, plantain and dandelion.

The broad spectrum herbicidal activity of these compounds suggests their use for the control or eradication of undesirable vegetation on industrial sites and on rail road ballast.

The concentration at which the compounds are to be used will naturally vary with the result desired, the type of vegetation, the formulation used, the mode of application, weather conditions, foliage density, and other similar factors. Since so many variables play a role, it is not possible to indicate a concentration suitable for all situations. Generally, however, when the compounds are used in pre-emergence treatments, they are applied at concentrations of from 0.25 to 35 pounds of active ingredient per acre. Concentrations of from 0.5 to 8 pounds per acre are preferred for selective weed control. When the compounds are used in soil-foliage applications, they are applied at concentrations of from 2 to 35 pounds per acre. More can be applied to control diflicult-to-kill species under adverse conditions.

Preferred for use as herbicides are the addition compounds of formula 1 where R is a A H:- l radical where A is methyl or ethyl, Y is hydrogen or methyl, and Z is alkyl or 1 through 6 carbon atoms; R is halogen, or a branched or unbranched alkyl of 1 through 6 carbon atoms;

R is hydrogen, or a branched or unbranched alkyl of 1 through 6 carbon atoms;

R is hydrogen;

X is oxygen; and

M is calcium;

with the proviso that R and R can be joined to form an alkylene bridge of 3 through 5 carbon atoms.

Especially preferred for use because of their herbicidal effectiveness are the calcium thiocyanate addition compounds with '3 l-lower alkylethyl -5-ha1ogeno-6-methyluracils 3-(2- lower alkylethyl) -5-halogeno-6-methylunacils 3-( l-lower alkylisopropyl) -5-halogeno-6-methyluracils 3 (cycloalkyl) -5-halogeno-6-methyluracils 3-(cycloalkenyl)-5-halogeno-6-methy!luracils 3 (phenyl) -5 halogeno-6-methyluracils 3-(bicycloalkyl)-5-halogeno-6-methyluracils 3- (bicycloal-kenyl) -5-halogeno-G-methyluracils '3- (tr-icycloalkyl) -5-halogeno-6-methyluracils 3 (tricyclo alkenyl) -S-halogeno-6-methyluracils 3-(lower alkyl) -5,6-alkyleneuracils and 3- (cycloalkyl) -5,6-alkyluracils In the foregoing list, lower .alkyl means an alkyl radical containing 1 through 4 carbon atoms.

The herbicidal compositions of this invention incorporating the uracil-thiocyanate addition compounds hereof can readily be prepared for use by incorporating them with suitable adjuvants. I

The'amount of addition compound in such preparations can vary over a wide nange according to need. Generally speaking, they will contain from about 0.5 to 95%, by weight of a uracil.

Powder and dust preparations can be made by mixing compounds of the invention with finely-divided solids such as tales, natural clays, pyrophillite, diatomaceous earth and synthetic fine silicas; flours such as walnut shell, wheat, redwood, s-oya bean and cotton seed; or inorganic substanoes such as magnesium carbonate, calcium silicate, calcium phosphate, sulfur and lime. These preparations are made by thoroughly blending the active ingredients and the solid. The particles in such preparations are preferably less than 50 microns in average diameter.

Granules and pellets can be made by mixing a finely- .divided addition compound with a suitable clay, moistening this mixture with from 15 to 20% by weight of water, and then extruding the mass through a suitable die under pressure. The extrusions are cut into pre-determined lengths and then dried. These pellets can be granulated if desired.

Granules can also be prepared by spraying a suspension or solution of an addition compound onto the surface of a preformed granule or clay, vermiculite or other suitable granular material. When the active material is applied to granules from a water suspension, it is preferable that a binding agent such as goulac, dextrin, swollen starch, glue or polyvinyl alcohol be added to attach it more firmly to the granule surfaces.

Emulsifiable oil preparations can be made by dissolving a uracil-thiocyanate addition compound in an oil such as isophorone or cyclohexanone, and adding an emulsifying agent.

Aqueous suspensions of those addition compounds which are water-insoluble (less than 0.1% at room temperature) are prepared by first making a slurry of the active ingredient and suitable dispersing agent and then wet-grinding this slurry, by ball-milling or sand-grinding, until 90% of the particles of active ingredient are less than 10 microns in diameter.

Both of these liquid preparations can be diluted to the proper concentrations with water before application.

The herbicidal preparations, whatever physical form they take, can also contain a surface-active agent. The

surfactant renders the preparations readily dispersible in liquids and improves their action on waxy leaves and the like. For general application, surface-active agents are used in the preparations at concentrations of from about 1 to 10%, by weight. Levels of from 0.5 to 6 parts of surfactant for each part of uracil, however, give unusual and unexpected results. Preparations having these higher levels of surfactants show greater herbicidal effectiveness than can be expected from a consideration of the activity of the components used separately.

The term surface-active agent is intended to include wetting agents, dispersing agents and emulsifying agents. Surface-active agents suitable for use are set forth in Detergents and Emulsifiers Up-to-Date, 1962. John W. McCutcheon, Inc., Morristo-wn, New Jersey. Other surface-active agents which can be used in these preparations are listed in US. Patents 2,139,276, 2,412,- 510, 2,426,417, 2,655,477, and Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the US. Department of Agriculture.

The preparations can also optionally contain adhesives such as gelatin, blood albumin and such resins as rosin alkyd resins. These increase retention and tenacity of deposits following application.

EXAMPLES To aid in practicing the invention, the following examples are presented:

Preparation of compounds EXAMPLE 1 One hundred fifty parts by volume of aqueous calcium thiocyanate solution (55-60%) are stirred at room temperature. To this are added 24.7 parts by weight of 5-bromo-3-isopropyl-o-methyluracil at room temperature. The temperature is increased from 25.5 C. to 27 C., and part of the uracil reactant dissolves, giving a milky solution. With additional stirring the product separates as a White paste.

After being stirred overnight, the product is filtered from the reaction mixture, washed with ether until the washings are colorless, and dried in a vacuum desiccator.

There are obtained 33 parts, by weight, of a white granular solid which melts above 300 C. It is soluble in acetone, acetonitrile and dimethylformamide.

This product is essentially pure 5-bromo-3-isopropyl- 6-methyl l/l addition compound with calcium thiocyanate.

EXAMPLE 2 3-isopropyl-6-methyluracil (25.2 parts by weight) is added, in one portion, to a stirred aqueous solution of parts, by volume, of calcium thiocyanate (SS-60%). The temperature increases from 25 C. to 29 C. in four minutes and the mixture becomes pastelike.

After being stirred overnight, the product is filtered from the reaction mixture and washed with ether and n-pentane. The solid is dried overnight in a vacuum desiccator to give 48.5 parts of the 3-isopropyl-6-methyluracil l/l addition compound with calcium thiocyanate having a melting point greater than 300 C.

EXAMPLE 3 1,6-dimethyl-3-isopropyl (18.2 parts by weight) is added, in one portion, to a stirred aqueous solution of 150 parts by volume of calcium thiocyanate (55-60%). After being stirred overnight, the product is filtered from the mixture and washed with n-pentane, ether and finally benzene. The yield is 10.4 parts of the 1,6-dimethyl-3- isopropyluracil 2/1 addition compound with calcium thiocyanate having a melting point greater than 300 C.

EXAMPLE 4 3-cyclohexyl-5,6-trimethyleneuracil (23.4 parts by weight) is added, in one portion, to ,a stirred aqueous solution of 150 parts by volume of calcium thiocyanate (SS-60%). The temperature increases from 24 to 25.5 C.

The product is filtered from the solution after it has been stirred overnight, washed with n-pentane and ether, and then dried in a vacuum desiccator. There are obtained 33.5 parts by Weight of the 3-cyclohexyl-5,6-trimethyleneuracil 2/1 addition compound with calcium thiocyanate. It is a tan powder, with a melting point greater than 300 C.

EXAMPLE 5 5 -bromo-6-methyl-3 -phenyluracil (28.1 parts by weight) is added to a stirred aqueous solution of 150 parts, by volume, of calcium thiocyanate (SS-60%) After being stirred overnight, the 5-bromo-6-methyl-3-phenyluracil 1/1 calcium thiocyanate addition compound is isolated by filtration It is washed with n-pentane and ether, and then dried in a vacuum desiccator.

EXAMPLE 6 Two hundred twenty-five parts, by volume, of an aqueous solution of barium thiocyanate (35-40%) are stirred at room temperature. To this, at room temperature, are added 24.7 parts, by weight of 5-bromo-3-isopropyl-6- methyluracil. The solution is stirred overnight and the 5-bromo-3-isopropyl-6-methluracil 1/1 addition compound with barium thiocyanate is isolated by filtering, washing with ether, and drying in a vacuum desiccator over calcium chloride.

EXAMPLE 7 One hundred eighty-five parts, by volume, of an aqueous solution of strontium thiocyanate (4550%) are stirred at room temperature. To this are added 24.7 parts by weight of S-bromo-3-isopropyl-6-methyluracil at room temperature.

After being stirred overnight, the reaction mixture is filtered. The solid is washed with ether and n-pentane, and then dried in a vacuum desiccator over phosphorous pentoxide.

The product is essentially pure 5-bromo-3-isopropyl-6- methyluracil 1/1 addition compound with strontium thiocyanate.

Using the general procedures set out in Examples l-7, one can prepare thiocyanate addition compounds with the uracils listed in the following table by reacting the uracil with the indicated thiocyanate, in the indicated proportions:

8 Three hundred twenty-four grams of this mixture are mixed with 277 cc. of 20-30 mesh Ottawa sand. This mixture is agitated for 30 minutes at an agitator speed of 2700 rpm. in a sand-mill of the kind described in US.

Weight in 5 Patent 2,581,414

The resulting composition, after separation from the sand by centrifugation, is a thixotropic liquid whose solids do not cake densely on the bottom of the container on extended storage.

10 A portion of this composition can be extended with water to form a nonfl-occulated stable suspension containing 0.220%, by weight, of the active ingredient. When applied in 60 gallons of water to an industrial area, this mixture, at a rate of to pounds per acre of ac- 15 tive ingredient, gives excellent control of such broad-leaf and grass weeds such as crabgrass, foxtail, lambs quarters, wild carrot, barnyard grass and seedling Johnson grass.

The 1:1 addition compounds in the following table can 20 be similarly formulated and used in herbicidally equivalent amounts:

3-benzyl-5-bromo-6-methyluracil addition compound with Ca(SCN) 3-norbornylmethyl-G-methyluracil addition compound with Ca(SCN) 3-norbornenylmethyl-6-met'hyluracil addition compound with Ca(SCN) 3-(5-bromonorbornyl)-6-methyluraci1 addition compound with Ca(SCN) 3 isopropyl-S-methoxymethyl-6-methyluracil addition compound with Mg(SCN) 3-isopropl-5-bromo-6-bromomethyluracil addition compound with Ca(SCN) 3-isopropyl-5-chloro-6-chloromethyluracil addition compound with C8.(SCN)2 EXAMPLE 9EMULSIFIABLE OIL Percent 1,6-dimethyl-3-isopropy-luracil 2/1 addition compound wit-h Ca(SCN) 10 Isophorone 85 Polyoxyethylene ether of alkylated phenol 5 This solution is extended with 200 gallons of water and applied at a rate of 25 pounds of active ingredient per acne for control of pepper grass, wild mustard, pigwe ed, crab grass and foxtail growing on an industrial site.

The addition compounds in the following table can be Thio- Volume and Strength cyanate Thiocyanate Solution VolumeinMl.

150 ml. (-60%) 150 ml. 55-60%) 150 ml. 55-60%) 150 ml. 55-60%) 150 ml. 55 150 mi. (55-60%) 150 ml. 55-60% 150 n11. 55-60% 225 ml 35-40% 185ml 5-56% 150 ml 55-60%) 150ml 5-60% 150 1111 (5560% 150ml 55-60% 150ml 55-66%) 150 ml 55-60%) 150ml 55-60% 150 ml. 55-60%) 150 ml. 55-60% 150 ml. 55-60%). 150 1111. 55-60%).

Herbz'cz'dal formulation EXAMPLE 8AQUEOUS SUSPENSION Percent 3-sec.-butyl-S-bromo-6-methyluracil 1/1 addition compound with Ca(SCN) 40.0

Attapulgite, hydrated 2.0 Goulac (sodium lignin sulfonate) 5.0 Water 53.0

similarly formulated and used, in herbicidally equivalent amounts:

3-allyl-6-methyluracil 1/1 addition compound with Oa(SCN) 3-propynyl-6-methyluraci-l 1/1 addition compound with Ca(SCN) 3-cyclohexenyl-6-methyluracil 1/1 addition compound with Ca(SCN) 1,3-diisopropyl-S-bromo-6-methyluracil 2/1 addition compound with Ca (SCN) EXAMPLE 10.GRANULES H Percent 5-bromo-3-sec-butyl-6methyluracil 1/ 1 addition compound with Ca(SCN) 10 California Ca, Mg sub-bentonite 75 Anhydrous sodium sulfate 1S EXAMPLE 1 1.PELLETS Percent 5 bromo-3-sec.-butyl-6 -methyluracil 1/1 addition cmpound with Ca(SCN) 11 Sodium sulfate, anhydrous 10 Mixtureof sodium 'lignin sulfonate and wood sugars 13 Sub-bentonite 33 Kaolinite 33 These ingredients are mixed and micropulverized.

Eighteen percent of water is added to this preparation, with mixing. The mixture is then extruded through a pellet machine to give -inch pellets, which are then dried to constant weight.

Two hundred pounds per acre of this formulation are applied along a fire lane for the control of quack grass barnyard grass, foxtails, crab grass, dandelion, wild mustard, pigweed and cocklebur.

The addition compounds in the following table can be similarly formulated and used, in herb-icidally equivalent amounts 3-(5-chloronorbornenyl) 6 methyluracil 1/1 addition compound with Ca(SCN) 3-isobutyl-5-nitro-6-methyluracil 1/1 addition compound with,Ba(SCN) 3-isopropyl-5 hydroxymethyl-6-methyluracil 1/1 addition compound with Sr(SCN) EXAMPLE 1'2.WETTABLE POWDER Percent -bromo-3-isopropyl-6-methyluraci1 1/ 1 addition compound with Ca(SCN) 95 Sodium. lignin sulfonate 3 Sodium alkyl aryl su'lfonate 2 These ingredients are mixed and micropulverizcd to an average particle size below 50 microns.

The "resulting wettable powder is applied at the rate of 8 pounds per :acre (active) in 25 gallons water for the control of wild oats and cheatgrass along roadsides.

The 3-sec.-butyl-5-chloro-6-methyluracil 1/ 1 addition compound with Ca(SCN) and the 3-(2-ethylpropyl)-5- bromo-6-methyluracil 1/1 addition compound with can be similarly formulated and used, in herbicidally equivalent amounts.

EXAMPLE 13.WETTABLE POWDER Percent 3-cyclohexyl-5,6trimethyleneuracil 2/1 addition compound with Ca(SCN) 80 Attapulgite clay 17 Methylated cellulose 2 Sodium dioctyl suifosuccinate 1 These ingredients are mixed and micropulverized to an average particle size below 50 microns.

Ten pounds (active) of this wettable powder in 40 gallons of water are sprayed around the edges of cultivated fields. Excellent control of foxtail, crab grass and barnyard grass is obtained.

The embodiments of the invention in which an exclusive property or privilege is claimed are: I

1. A herbicidal composition comprising an adjuvant and, in an amount sufiicient to exert herbicidal action, a compound of the formula litgn where R is selected from the group consisting of alkyl of 1 through 10 carbon atoms, substituted alkyl of 1 through 8 carbon atoms, wherein said substituent is selected from the group consisting of bromide, chlorine, hydroxy, alkoxy, alkoxycar bonyl, dialkylamino, and cyano,

aryl of 5 through 10 carbon atoms,

substituted cycloalkyl of 3 through 12 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, bromine, fluorine, phenylalkyl of 1 through 6 carbon atoms, chloroa-lkoxy of 1 through 5 carbon atoms, trifluoromethyl, 1,2- tetramethylene, and 1,2-trimethylenylene,

arylalkyl of 5 through 13 carbon atoms,

substituted arylalkyl of 5 through 13 carbon atoms, wherein said substituent is selected from the group consisting of chlorine, nitro, alkyl and alkoxy,

alkenyl of 3 through 8 car-bon atoms,

alkynyl of 3 through 8 carbon atoms,

cycloalkyl of 3 through 12 carbon atoms,

substituted cycloalkyl of 3 through 12 carbons atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and

alkyl,

cycloalkenyl of 4 through 12 carbon atoms,

substituted cycloalkenyl of 3 through 12 carbon atoms wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy, and alkyl,

cycloalkyl alkyl of 4 through 13 carbon atoms,

(substituted cycloalkyl)alkyl of 4 through 13 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy and alkyl,

cycloalkenyl of 5 through 13 carbon atoms,

(substituted cycloalkenyDalkyl of 5 through 14 carbon atoms, wherein said substituent is selected from the group consisting of bromine, chlorine, methoxy and alkyl;

R is selected from the group consisting of hydrogen, halogen, nitro, 'hydroxymethyl, alkyl of 1 through 6 carbon atoms, and a-lkoxymethyl wherein the alkoxy portion thereof contains 1 through 4 carbon atoms;

R is selected from the group consisting of hydrogen,

methyl, chloromethyl, and bromomethyl;

R is selected from the group consisting of hydrogen and alkyl of 1 through 4 carbon atoms;

X is selected from the group consisting of oxygen and sulfur;

1 1 1 2 M is selected from the group consisting of magnesium, References Cited by the Examiner calcium, strontium and barium; and UNITED STATES PATENTS n is selected from the group consisting of 1 and 2. 2. The composition of claim 1 wherein the adjuvant 2992089 7/1961 Melander at 71-25 is a surfactant. 5r FOREIGN PATENTS 3. The composition of claim 1 wherein the adjuvant 1,270,771 7/1961 France.

is a finely divided dispersilmle solid.

4. The composition of claim l wherein the adjuvant LEWIS GOTTS Pr'mary Exammer' is a liquid. JAMES O. THOMAS, JR., Examiner. 

1. A HERBICIDAL COMPOSITION COMPRISING AN ADJUVANT AND, IN AN AMOUNT SUFFICIENT TO EXERT HERBICIDAL ACTION, A COMPOUND OF THE FORMULA 